WO2023182686A1 - Polylactide resin composition with excellent crystallinity, and preparation method therefor - Google Patents

Abstract

The present invention relates to a polylactide resin composition using combined specific nucleating agents, the composition having excellent crystallinity and excellent dispersibility between components so as to also have excellent transparency, and thus can maintain the inherent properties of a polylactide resin according to the present invention while having excellent processability.

Description

Polylactide resin composition with excellent crystallinity, and method for producing the same

Cross-Citation with Related Application(s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0035552, dated March 22, 2022, and all contents disclosed in the documents of the Korean patent applications are included as part of this specification.

The present invention relates to a polylactide resin composition with excellent crystallinity and a method for producing the same.

Polylactide (or polylactic acid; PLA) resin is manufactured based on bio-based materials, and is an eco-friendly material that emits less carbon dioxide, a global warming gas, during the manufacturing process and has the characteristic of being decomposed at a specific temperature and in composting facilities. am. In addition, it has recently been attracting attention as one of the materials that can replace existing crude oil-based resins as a response to waste plastic use and carbon emission regulations.

In addition, polylactide resin has the advantage of being cheaper than other biodegradable polymers and having high tensile strength and modulus characteristics.

However, polylactide resin has a rigid polymer main chain repeated in short units, has a slow crystallization rate due to slow chain mobility, has a long molding cycle, and thus has a problem of low productivity. Therefore, in order to improve these problems, much research is being conducted to improve productivity and heat resistance by introducing substances such as nucleating agents.

Generally, the material used as the nucleating agent is mainly an inorganic nucleating agent, and materials such as talc, mica, and nanoclay are used, and some of them can be added during PLA molding to improve heat resistance and strength. It has been reported that it can be done. However, if these nucleating agents are added in excessive amounts, there is a problem of increased resin specific gravity and decreased transparency. Meanwhile, organic nucleating agents such as LAK 301 (aromatic sulfonate drivate), sodium benzoate, N-aminophthalimide, phthalhydrazide, and cadmium phenylmalonate are used as substances to improve crystallinity and transparency. However, these materials are not bio-based and have dispersion issues with PLA resin.

Therefore, there is a need to introduce a bio-based organic nucleating agent that can be manufactured as an eco-friendly product and at the same time does not impair transparency. In addition, it is necessary to further improve the crystallinity of polylactide resin by introducing a nucleating agent that has fewer dispersion problems.

The present invention is intended to provide a polylactide resin composition with excellent crystallinity by using a combination of specific nucleating agents.

Additionally, the present invention relates to a method for producing the polylactide resin composition.

In order to solve the above problems, the present invention provides the following polylactide resin composition:

polylactide resin; first nucleating agent; And a second nucleating agent,

The first nucleating agent is uracil or orotic acid,

The second nucleating agent is a compound containing a lactide oligomer structure,

Polaractide resin composition.

The term “polylactide resin” used in the present invention is defined to encompass a homopolymer or copolymer containing the following repeating units.

The polylactide resin may be manufactured by including the step of forming the repeating unit by ring-opening polymerization of a lactide monomer, and the polymer after the ring-opening polymerization and the forming process of the repeating unit are completed is called the “polylactide resin.” It can be referred to as ".

At this time, “lactide monomer” can be defined as follows. Typically, lactide can be divided into L-lactide made of L-lactic acid, D-lactide made of D-lactic acid, and mesolactide made of one L-form and one D-form. Additionally, a 50:50 mix of L-lactide and D-lactide is called D,L-lactide or rac-lactide. Among these lactides, it is known that if polymerization is performed using only L-lactide or D-lactide with high optical purity, L- or D-polylactide (PLLA or PDLA) with very high stereoregularity can be obtained. Lactide is known to have a faster crystallization rate and higher crystallization rate than polylactide, which has low optical purity. However, in this specification, “lactide monomer” is defined to include all forms of lactide, regardless of differences in the characteristics of each form of lactide and the characteristics of the polylactide resin formed therefrom.

Meanwhile, the polylactide resin according to the present invention has, for example, a weight average molecular weight of 70,000 to 400,000.

The present invention is characterized by improving the crystallinity of the polylactide resin by using the first and second nucleating agents together in the polylactide resin.

The first nucleating agent is uracil or orotic acid. The first nucleating agent is a bio-based organic material that can be added to polylactide resin to act as a nucleation site and increase the crystallization rate by causing crystal nucleation at a high temperature.

Preferably, the first nucleating agent is included in an amount of 0.1 to 5% by weight based on the total weight of the polylactide resin composition. If the content is less than 0.1% by weight, the effect of using the first nucleating agent is insignificant, and if the content exceeds 5% by weight, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the first nucleating agent is 0.2% by weight or more, 0.3% by weight, 0.4% by weight, or 0.5% by weight or more relative to the total weight of the polylactide resin composition; 4.5 weight percent or less, 4.0 weight percent or less, or 3.5 weight percent or less.

The second nucleating agent is a nucleating agent containing an oligomeric structure of lactide monomer. Due to the oligomeric structure of the lactide monomer, it has high compatibility with polylactide resin and is added to polylactide resin to play a role similar to a plasticizer. Accordingly, the degree of crystallinity can be increased by forming a free volume within the polylactide resin and improving the chain mobility of the polylactide resin.

Preferably, the second nucleating agent is a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

L is any one selected from the group consisting of:

In the above,

n1 is an integer from 1 to 4,

n2 is an integer from 1 to 4,

n3 is an integer from 1 to 30,

R is a substituent represented by the following formula (2),

[Formula 2]

n represents the number of repeat units,

R' is hydrogen or acetyl.

The weight average molecular weight of the second nucleating agent can be adjusted depending on the number of each lactide repeating unit. Preferably, the weight average molecular weight of the second nucleating agent is 1,000 to 50,000. More preferably, the weight average molecular weight of the second nucleating agent is 1,100 or more, 1,200 or more, 1,300 or more, 1,400 or more, or 1,500 or more; It is 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 9,000 or less, or 8,000 or less.

Preferably, the second nucleating agent is included in an amount of 3 to 25% by weight based on the total weight of the polylactide resin composition. If the content is less than 3% by weight, the effect of using the second nucleating agent is insignificant, and if the content exceeds 25% by weight, there is a risk of impairing the inherent physical properties of the polylactide resin. More preferably, the second nucleating agent is 3.5 wt% or more, 4.0 wt% or more, or 4.5 wt% or more based on the total weight of the polylactide resin composition; It is included in not more than 24% by weight, not more than 23% by weight, not more than 22% by weight, or not more than 21% by weight.

On the other hand, the method for producing the polaractide resin composition according to the present invention described above is not particularly limited as long as it is a method of mixing the polylactide resin described above, the first nucleating agent, and the second nucleating agent. For example, since each of the above components is well soluble in CHCl ₃ solvent, it can be prepared by dissolving each component in each CHCl ₃ solvent, mixing them, and then removing the solvent.

The polaractide resin composition according to the present invention described above has excellent crystallinity and excellent dispersibility between each component, so it also has excellent transparency. Therefore, the polaractide resin composition according to the present invention has excellent processability and can maintain the inherent properties of the polaractide resin according to the present invention.

Figure 1 shows the NMR results of the second nucleating agent prepared in Preparation Example 1.

Figures 2 to 5 show DSC measurement results for polylactide resin compositions prepared in Examples and Comparative Examples.

Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples only illustrate embodiments of the present invention, and the content of the present invention is not limited by the following examples.

Preparation Example 1: Second nucleating agent (P4-oligomer preparation)

1) Preparation of second nucleating agent (P4-O-oligomer)

An oligomer was prepared using PEG-400 (P4) as an initiator. Specifically, add Lactide:P4 to a 20 mL vial for a total of 4.5 g at a molar ratio of 4:1, 8:1, 12:1, and 16:1, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named P4-O-001, P4-O-002, P4-O-003, and P4-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

2) Preparation of second nucleating agent (P4-A-oligomer)

An oligomer was prepared using PEG-400 (P4) as an initiator. Specifically, add Lactide:P4 to a 20 mL vial for a total of 4.5 g at a molar ratio of 4:1, 8:1, 12:1, and 16:1, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After adjusting the temperature to 120°C, acetic anhydride (4 equivalents compared to the terminal OH group) was added, and the reaction proceeded for an additional 12 hours. After completion of the reaction, by-product acetic acid and residual acetic anhydride were removed by vacuum drying to prepare a second nucleating agent having a structure in which the terminal group was substituted with an acetyl group, which were P4-A-001, P4-A-002, and P4-A, respectively. They were named -003 and P4-A-004, and the weight average molecular weight is shown in Tables 1 and 2 below.

NMR analysis was performed on the second nucleating agent prepared above along with PEG-400, the starting material, and the results are shown in Figure 1.

As shown in Figure 1, OH groups (2.5 ppm) or Acetyl groups (2.1-2.2 ppm) were observed at both ends of the oligomer.

Preparation Example 2: Second nucleating agent (P10-oligomer preparation)

1) Preparation of the second nucleating agent (P10-O-oligomer)

An oligomer was prepared using PEG-1000 (P10) as an initiator. Specifically, add Lactide:P10 at a molar ratio of 4:1, 8:1, 12:1, and 16:1 to a 20 mL vial for a total of 4.5 g, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named P10-O-001, P10-O-002, P10-O-003, and P10-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

2) Preparation of the second nucleating agent (P10-A-oligomer)

An oligomer was prepared using PEG-1000 (P10) as an initiator. Specifically, add Lactide:P10 at a molar ratio of 4:1, 8:1, 12:1, and 16:1 to a 20 mL vial for a total of 4.5 g, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After adjusting the temperature to 120°C, acetic anhydride (4 equivalents compared to the terminal OH group) was added, and the reaction proceeded for an additional 12 hours. After completion of the reaction, by-product acetic acid and residual acetic anhydride were removed by vacuum drying to prepare a second nucleating agent having a structure in which the terminal group was substituted with an acetyl group, which were P10-A-001, P10-A-002, and P10-A, respectively. They were named -003 and P10-A-004, and the weight average molecular weight is shown in Tables 1 and 2 below.

Preparation Example 2: Second nucleating agent (CD-oligomer preparation)

The oligomer was prepared using cyclohexanedimethanol (CD) as an initiator. Specifically, add Lactide:CD at a molar ratio of 4:1, 8:1, 12:1, and 16:1 to a 20 mL vial for a total of 4.5 g, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named CD-O-001, CD-O-002, CD-O-003, and CD-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

Preparation Example 3: Second nucleating agent (PD-oligomer preparation)

An oligomer was prepared using 1,5-pentanediol (PD) as an initiator. Specifically, add Lactide:PD to a 20 mL vial for a total of 4.5 g at a molar ratio of 4:1, 8:1, 12:1, and 16:1, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named PD-O-001, PD-O-002, PD-O-003, and PD-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

Preparation Example 4: Second nucleating agent (DG-oligomer preparation)

The oligomer was prepared using diethylene glycol (DG) as an initiator. Specifically, add Lactide:DG to a 20 mL vial for a total of 4.5 g at a molar ratio of 4:1, 8:1, 12:1, and 16:1, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named DG-O-001, DG-O-002, DG-O-003, and DG-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

Preparation Example 5: Second nucleating agent (GL-oligomer preparation)

An oligomer was prepared using glycerol (GL) as an initiator. Specifically, add Lactide:GL at a molar ratio of 6:1, 12:1, and 18:1 (molar ratio) to a 20 mL vial for a total of 4.5 g, and add 0.1 to 0.2 wt% of Sn(Oct) ₂ catalyst. After adding as much as possible, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named GL-O-001, GL-O-002, and GL-O-003, respectively, and the weight average molecular weights are shown in Tables 1 and 2 below.

Preparation Example 6: Second nucleating agent (PT-oligomer preparation)

An oligomer was prepared using pentaerythritol (PT) as an initiator. Specifically, add Lactide:PT at a molar ratio of 8:1, 16:1, 24:1, and 32:1 to a 20 mL vial for a total of 4.5 g, and add 0.1 to 0.1 to 0.1 Sn(Oct) ₂ catalyst. After adding it to 0.2 wt%, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named PT-O-001, PT-O-002, PT-O-003, and PT-O-004, respectively, and the weight average molecular weight is shown in Table 1 below. and 2.

Preparation Example 7: Second nucleating agent (SB-oligomer preparation)

An oligomer was prepared using sorbitol (SB) as an initiator. Specifically, add Lactide:SB to a 20 mL vial for a total of 4.5 g at a molar ratio of 12:1, 24:1, and 36:1 (molar ratio), and add 0.1 to 0.2 wt% of Sn(Oct) ₂ catalyst. After adding as much as possible, it was reacted at 130°C for 4 hours. After vacuum drying and cooling to room temperature, a second nucleating agent was prepared, which was named SB-O-001, SB-O-002, and SB-O-003, respectively, and the weight average molecular weights are shown in Tables 1 and 2 below.

Examples and Comparative Examples

300 g of PLA pellet (4032D from NatureWorks; weight average molecular weight approximately 200,000) was placed in a 500 mL vial, and 12 mL of CHCl ₃ was added to completely dissolve it. The first and second nucleating agents shown in Table 1 below were dissolved or evenly dispersed in 4 mL of CHCl ₃ depending on their respective contents to prepare a solution, and then mixed with the PLA solution prepared previously. The solution mixed evenly by sonication for 1 hour was naturally dried on an Al dish (diameter: 80 mm) to remove the solvent, and then dried in vacuum at 60°C for 5 hours to form a PLA film (thickness: about 0.5 mm to 1.0 mm). were prepared respectively.

Experiment example

The physical properties of the first nucleating agent, second nucleating agent, and PLA film prepared above were measured by the following method.

1) Weight average molecular weight

Using GPC (Gel Permeation Chromatography) equipment, the number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated, and the oligomer molecular weight distribution (Mw/Mn) was measured. The specific measurement conditions are as follows.

- Column: PLgel Mixed E x 2

- Solvent: THF

- Flow rate: 0.7 mL/min

- Sample concentration: 3.0 mg/mL

- Injection volume: 100 μl

- Column temperature: 40℃

- Detector: Waters 2414 RID

- Standard: PS (polystyrene)

2) DSC (differential scanning calorimetry)

In order to make the PLA film completely amorphous and erase the heat history, it was heated to 250℃, which is above the melting temperature of PLA, at a heating rate of 10℃/min, and then stabilized for 5 minutes to create an amorphous molten state. Then, in order to analyze ΔHc and crystallization behavior, it was cooled to -20°C at a cooling rate of 10°C/min and the crystallization peak was observed. After stabilization, in order to observe the melting peak, it was reheated ( ^2nd Run) at a rate of 10°C/min to 250°C and ΔHm at the melting peak was confirmed. Crystallinity X was calculated using the following equation (100% crystalline PLA ΔHm = 93 J/g).

- Crystallinity during cooling: (heating peak area during cooling, ΔHc) / (100% crystalline PLA ΔHm)

- 2 ^nd Run crystallinity: (Area of endothermic peak in 2 ^nd thermogram, ΔHm-cold crystallization exothermic peak area, ΔHcc) / (100% crystalline PLA ΔHm) * 100

The results are shown in Tables 1 and 2 below, and some of the DSC measurement results are shown in Figures 2 to 5. Meanwhile, in Tables 1 and 2 below, the meaning of each abbreviation is as follows.

D-SB(D-Sorbitol), PT(pentaerythritol), OA(Orotic acid), L-PA(L-phenylalanine), PH(phthalhydrazide)

item	first nuclear system		second nuclear system			DSC (cooling)		DSC (second temperature increase)
	type	wt%	type	Mw	wt%	Tc( oC )	Xc(%)	Tg( oC )	Tcc( oC )	Tm( oC )	Xc(%)
Example 1	Uracil	One	CD-O-001	1,200	10	112.3	5.1	50.3	101.9	165.2	5.7
Example 2	Uracil	One	PD-O-001	1,200	10	111.2	5.1	48.4	99.0	164.5	9.7
Example 3	Uracil	One	PD-O-001	1,200	20	102.8	30.5	31.4	83.2	153.6	39.3
Example 4	Uracil	One	DG-O-001	1,200	10	112.6	5.7	50.2	101.2	164.6	6.8
Example 5	Uracil	One	DG-O-001	1,200	20	99.6	20.2	36.0	88.9	154.4	22.1
Example 6	Uracil	One	P4-O-001	1,600	10	115.1	12.3	44.9	92.0	165.4	19.6
Example 7	Uracil	One	P4-O-001	1,600	20	102.0	34.0	37.0	77.5	162.9	54.6
Example 8	Uracil	One	P10-O-001	2,500	10	103.7	16.0	43.8	88.0	166.4	25.4
Example 9	Uracil	One	P10-O-001	2,500	20	103.7	38.6	-	-	164.3	52.6
Example 10	OA	One	CD-O-001	1,200	10	100.8	4.9	52.7	109.0	166.8	8.2
Example 11	OA	One	PD-O-001	1,200	10	101.4	16.0	50.7	104.7	166.9	27.2
Example 12	OA	One	DG-O-001	1,200	10	102.2	13.9	47.0	101.0	165.7	23.2
Example 13	OA	One	P4-O-001	1,600	10	100.7	22.9	45.9	95.6	166.4	39.0
Example 14	OA	One	P10-O-001	2,500	10	96.9	24.2	42.4	87.3	166.9	41.4
Example 15	Uracil	3	P4-A-001	1,600	10	112.2	20.2	46.0	98.4	165.7	25.7
Example 16	OA	3	P4-A-001	1,600	10	98.3	11.4	47.0	100.6	167.0	17.4
Example 17	Uracil	3	P4-A-002	5,100	10	112.3	19.1	55.0	109.2	167.4	25.0
Example 18	OA	3	P4-A-002	5,100	10	103.4	7.2	55.3	110.1	168.2	11.2
Example 19	Uracil	3	P4-A-003	800	10	105.6	43.4	-	-	157.3	52.4
Example 20	OA	3	P4-A-003	800	10	107.7	45.0	-	-	158.1	52.4
Example 21	Uracil	3	P4-A-004	1,000	10	111.6	37.9	-	-	162.2	47.9
Example 22	OA	3	P4-A-004	1,000	10	96.7	38.3	-	-	159.5	46.4
Example 23	Uracil	3	P10-A-001	2,500	5	115.0	44.5	-	-	162.8	51.9
Example 24	Uracil	One	P10-A-001	2,500	10	109.8	47.3	-	-	160.6	55.1
Example 25	OA	One	P10-A-001	2,500	10	95.0	39.2	-	-	160.1	54.4
Example 26	Uracil	3	P10-A-001	2,500	10	117.8	27.5	43.3	92.6	166.7	37.8
Example 27	OA	3	P10-A-001	2,500	10	98.6	21.7	43.7	94.3	167.5	35.3
Example 28	Uracil	3	P10-A-002	6,000	10	116.1	27.2	52.2	106.2	167.3	35.2
Example 29	OA	3	P10-A-002	6,000	10	100.7	12.2	53.2	105.7	168.2	18.3
Example 30	Uracil	3	P10-A-003	1,800	10	106.2	45.5	-	-	157.7	53.3
Example 31	OA	3	P10-A-003	1,800	10	112.5	48.6	-	-	159.9	56.8
Example 32	Uracil	3	P10-A-004	2,000	10	104.3	44.8	-	-	157.5	54.3
Example 33	OA	3	P10-A-004	2,000	10	100.2	42.9	-	-	159.2	54.6

item	first nuclear system		second nuclear system			DSC (cooling)		DSC (second temperature increase)
	type	wt%	type	Mw	wt%	Tc( oC )	Xc(%)	Tg( oC )	Tcc( oC )	Tm( oC )	Xc(%)
Comparative Example 1	-	-	-	-	-	95.1	0.2	60.1	124.1	165.4	3.4
Comparative Example 2	Talc	3	-	-	-	98.7	3.7	59.3	118.6	165.9	7.6
Comparative Example 3	Talc	10	-	-	-	101.7	12.3	59.3	110.0	166.5	19.1
Comparative Example 4	D-SB	3	-	-	-	92.4	0.6	57.3	116.8	163.5	1.7
Comparative Example 5	P.T.	3	-	-	-	91.8	0.4	57.5	116.1	166.8	0.3
Comparative Example 6	Uracil	3	-	-	-	111.7	11.5	59.8	123.2	165.9	15.1
Comparative Example 7	OA	3	-	-	-	109.8	3.0	59.9	127.0	166.6	4.5
Comparative Example 8	L-PA	3	-	-	-	92.9	1.1	59.0	122.3	165.5	4.4
Comparative Example 9	PH	3	-	-	-	102.8	2.7	58.3	113.9	164.2	5.7
Comparative Example 10	-	-	GL-O-001	1,700	10	90.5	0.8	54.4	119.1	166.8	2.0
Comparative Example 11	-	-	GL-O-002	3,800	10	91.4	0.8	55.9	118.4	167.5	1.9
Comparative Example 12	-	-	GL-O-003	5,400	10	91.1	0.5	56.9	123.1	168.1	1.6
Comparative Example 13	-	-	PT-O-001	2,100	20	83.5	2.3	42.9	98.5	157.8	3.5
Comparative Example 14	-	-	SB-O-001	2,800	20	86.4	0.2	47.4	107.1	159.5	0.7
Comparative Example 15	-	-	CD-O-001	1,200	20	85.3	2.6	38.7	89.7	155.6	3.9
Comparative Example 16	-	-	PD-O-001	1,200	20	87.3	5.4	35.0	83.6	154.5	13.9
Comparative Example 17	-	-	DG-O-001	1,200	20	87.4	3.1	39.5	90.3	154.8	9.3
Comparative Example 18	-	-	P4-O-001	1,600	20	82.7	16.9	32.0	79.4	162.9	31.9
Comparative Example 19	-	-	P10-O-001	2,500	20	85.7	30.7	-	-	164.6	52.3
Comparative Example 20	-	-	P4-A-001	1,600	10	-	-	47.5	100.5	166.0	0.8
Comparative Example 21	-	-	P4-A-002	5,100	10	-	-	55.5	111.1	167.7	0.3
Comparative Example 22	-	-	P10-A-001	2,500	10	88.8	3.0	42.9	93.2	1666.8	4.1
Comparative Example 23	-	-	P10-A-002	6,000	10	-	-	52.7	106.2	167.8	0.2
Comparative Example 24	Talc	One	GL-O-001	1,700	10	91.8	11.3	52.0	101.8	163.1	18.4
Comparative Example 25	Talc	One	PT-O-001	2,100	10	91.6	9.8	50.6	101.4	159.5	15.3
Comparative Example 26	Talc	One	SB-O-001	2,800	10	90.1	1.0	49.2	107.1	152.0	2.4
Comparative Example 27	Talc	One	CD-O-001	1,200	10	88.9	12.9	48.7	99.6	159.5	21.3
Comparative Example 28	Talc	One	PD-O-001	1,200	10	89.5	20.6	44.4	93.7	160.7	34.5
Comparative Example 29	Talc	One	DG-O-001	1,200	10	90.2	15.9	47.4	97.0	162.4	28.1
Comparative Example 30	Talc	One	P4-O-001	1,600	10	100.3	37.5	41.8	-	164.8	48.8
Comparative Example 31	Talc	One	P10-O-001	2,500	10	94.3	29.1	-	-	164.9	43.2

As shown in Tables 1 and 2 above, in the case of the example in which the first and second nucleating agents were used simultaneously according to the present invention, it was confirmed that the crystallization temperature and crystallization were improved even with a small amount.

On the other hand, when the nucleating agent was not used (Comparative Example 1), when only the first nucleating agent was used (Comparative Examples 2 to 9), or when only the second nucleating agent was used (Comparative Examples 10 to 27), the crystallinity was low, and the second nucleating agent was used. However, when Talc was used as the first nucleating agent (Comparative Examples 28 to 36), the crystallization temperature was low.

Claims (8)

1. polylactide resin; first nucleating agent; And a second nucleating agent,

   The first nucleating agent is uracil or orotic acid,

   The second nucleating agent is a compound containing a lactide oligomer structure,

   Polaractide resin composition.
2. According to paragraph 1,

   The weight average molecular weight of the polylactide resin is 70,000 to 400,000,

   Polaractide resin composition.
3. According to paragraph 1,

   The first nucleating agent contains 0.1 to 5% by weight based on the total weight of the polylactide resin composition,

   Polaractide resin composition.
4. According to paragraph 1,

   The first nucleating agent contains 0.5 to 3.5% by weight based on the total weight of the polylactide resin composition,

   Polaractide resin composition.
5. According to paragraph 1,

   The second nucleating agent is a compound represented by the following formula (1),

   Polaractide resin composition:

   [Formula 1]

   

   In Formula 1,

   L is any one selected from the group consisting of:

   

   In the above,

   n1 is an integer from 1 to 4,

   n2 is an integer from 1 to 4,

   n3 is an integer from 1 to 30,

   R is a substituent represented by the following formula (2),

   [Formula 2]

   

   n represents the number of repeat units,

   R' is hydrogen or acetyl.
6. According to paragraph 1,

   The weight average molecular weight of the second nucleating agent is 1,000 to 50,000,

   Polaractide resin composition.
7. According to paragraph 1,

   The second nucleating agent is contained in an amount of 3 to 25% by weight based on the total weight of the polylactide resin composition,

   Polaractide resin composition.
8. According to paragraph 1,

   The second nucleating agent is contained in an amount of 4.5 to 21% by weight based on the total weight of the polylactide resin composition.

   Polaractide resin composition.

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